Miscibility of otherwise immiscible compounds

ABSTRACT

The present invention relates to a novel method for compatibilizing, i.e. improving miscibility of, otherwise immiscible organic materials highly useful in the fibers industry, as well as the compatibilized product of the method. These compatibilized products are stable in the liquid phase at temperatures ranging from about 40° C. to about 200° C. The method involves use of a glycol derived from polymerization of alkylene oxide and tetrahydrofuran, the alkylene oxide having from 2 to 4 carbon atoms, i.e. poly(tetramethylene-co-alkyleneether) glycol, in the mixture.

BACKGROUND OF THE INVENTION

The present invention relates to a novel method for compatibilizing,i.e. improving miscibility of, otherwise immiscible organic materialshighly useful in, for example, the fibers industry, as well as thecompatibilized product of the method. These compatibilized products arestable in the liquid phase at temperatures ranging from about 40° C. toabout 200° C., more specifically from about 50° C. to about 100° C.,depending on the phase separation transition and decompositiontemperatures of the individual components of the compatibilized product.The method involves use of a glycol derived from polymerization ofalkylene oxide and tetrahydrofuran (THF), the alkylene oxide having from2 to 4 carbon atoms, i.e., poly(tetramethylene-co-alkyleneether) glycol,especially such a copolymer specially manufactured as herein described.The glycol derived from polymerization of alkylene oxide and THF may bereferred to herein as an alkylene oxide copolymer. Non-limiting examplesof such alkylene oxide copolymers for use herein include thepoly(tetramethylene-co-alkyleneether) glycols derived from one alkyleneoxide, e.g. ethylene oxide (EO), molecule and two THF molecules; onealkylene oxide, e.g. EO, molecule and three THF molecules, etc.

Mixtures of short chain glycols with long chain polyols, and polyetherswith polyesters, normally immiscible or rapidly losing miscibility attemperatures within the range of from about 40° C. to about 100° C. havea variety of important commercial uses. For example, ethylene glycol(EG) and butanediol (BDO) are generally immiscible with polyetherpolyols such as polytetramethylene ether glycol (PTMEG) at thesetemperatures. Such mixtures are important commercially for thepreparation of polyurethane elastomers, coatings and adhesives by thereaction of this mixture with one or more diisocyanates and assortedadditives. Further, polyethylene glycol (PEG) and polypropylene glycol(PPG) are generally immiscible with polyether polyols such aspolytetramethylene ether glycol (PTMEG) at these temperatures. Theselater mixtures are important commercially for the preparation ofmoisture permeable or absorbent articles. Mixtures of polyethers such asPTMEG and polypropylene glycol (PPG) with polyesters such aspolycaprolactone glycol (PCLG) are generally immiscible at thesetemperatures and they are commercially useful for making a broad rangeof elastomers and coatings requiring ether and ester properties.

Due to the importance of these compounds being compatible in mixture attemperatures within the range of from about 40° C. to about 100° C. orhigher, researchers have tried to effect compatibility by a variety ofdifferent methods. For example, techniques have been described forsolubilizing some of these mixtures for commercial applications, butthey have troublesome shortcomings or deficiencies which createprocessing and handling problems which add to costs for production of;for example, polyurethane elastomers, coatings, adhesives and foams.

U.S. Pat. No. 4,226,756 describes compositions of polyols and ethyleneglycol in which the polyol contains internal oxyethylene andoxypropylene groups and additional oxyethylene end groups. Thesecompositions are limited to polyols with a polyoxypropylenepolyoxyethylene glycol structure. Additionally, the balance ofoxyethylene internal and end groups is an important variable in thefunction of the materials as compatibilizers.

U.S. Pat. No. 4,385,133 describes a process for the preparation ofpolyurethane in which a low molecular weight glycol is rendered misciblein a polyol mixture by employing two polyoxypropylene polyoxyethylenepolyols of varying molecular weight and ethylene oxide (EO) content.This process requires the presence of two polyoxypropylenepolyoxyethylene glycols of different molecular weights and oxyethylenecontent.

U.S. Pat. No. 6,063,308 details a process for making a homogeneousmixture of curative, polyol, and other materials by allowing the mixtureto react with a small amount of a diisocyanate and a 2° or 3° amine.This process is of limited utility because the components must undergo achemical reaction in order to become homogeneous and requires intensivemixing. It is likely that the desired reaction product is also of ahigher viscosity than the starting materials, and is not described orcharacterized.

U.S. Pat. No. 6,093,342 teaches a variation of the process of above U.S.Pat. No. 6,063,308 in which two immiscible high molecular polyols andoptionally a low molecular weight glycol are compatibilized by allowingthe mixture to react with a small amount of a diisocyanate and a 2° or3° amine. This process also requires intensive mixing so that thematerials can react chemically. The uncharacterized composition productof this reference must be higher in viscosity than the startingmaterials, and is not described or characterized. Processes forhomogenizing mixtures of polyether and polyester are also described.

The techniques of the above patent references have serious commerciallimitations in that they are restricted to a particular class of polyols(polyoxypropylene polyoxyethylene polyols) or they entail the use ofreactive components and efficient mixing of the incompatible componentswhich is complicated and nontrivial on a large commercial scale. None ofthese references teach or suggest a method for preparing acompatibilized mixture of otherwise immiscible organic materials stablein the liquid phase at temperatures ranging from about 40° C. to about200° C., more specifically from about 50° C. to about 100° C., dependingon the phase separation transition and decomposition temperatures of thecomponents of the compatibilized product, or the compatibilizedcomposition comprising a glycol derived from polymerization of alkyleneoxide and tetrahydrofuran (THF), the alkylene oxide having from 2 to 4carbon atoms, i.e. poly(tetramethylene-co-alkyleneether) glycols. Thesecompatibilized compositions have the unique combination of propertiesdisclosed herein, such as, by way of non-limiting examples, remaininghomogeneous in the temperature range of from about 40° C. to about 200°C., more specifically from about 50° C. to about 100° C., so that theyare easy to handle in a commercial environment and can be used withoutagitation. These compositions can produce polymers with propertiescomparable to those made from difficult to handle, incompatiblecomponents.

SUMMARY OF THE INVENTION

Accordingly, it is desirable to provide a method for compatibilizing orimproving miscibility of otherwise immiscible organic materials highlyuseful in, for example, the coatings, adhesives, sealant, and elastomerindustries, as well as the compatibilized product of the method. Whenused as an elastomeric soft segment, such as for cast polyurethanewheels and rollers, the novel compatibilized product of the presentinvention will have well-balanced tensile properties, tear properties,and dynamic properties as well as desirable processing characteristics.Another advantage of such a compatibilized product may be to enablemanufacture of low temperature processed products having uniqueproperties.

Therefore, important embodiments of the present invention provide novelcompatibilized products comprising a mixture of short chain glycols withlong chain polyols, and polyethers with polyesters, normally immiscibleor rapidly losing miscibility at temperatures within those required inthe industry, such as, for example, from about 40° C., below the phaseseparation transition temperatures of some glycols, to the temperatureat which component decomposition occurs, such as, for example, about200° C. The compatibilized products resulting from the present inventionhave unique combinations of properties, along with miscibility attemperatures within the industry useful range of from about 40° C. toabout 200° C., more specifically from about 50° C. to about 100° C.,depending on the phase separation transition and decompositiontemperatures of the individual components of the compatibilized product,said properties including uniform viscosity and density, as well as longand useful shelf life.

More specifically, an important embodiment of the present invention is acompatibilized product comprising a mixture of ethylene glycol (EG)and/or butanediol (BDO) with polyether polyols such as, for example,polytetramethylene ether glycol (PTMEG), polypropylene glycol (PPG)and/or polycaprolactone glycol (PCLG), at these temperatures.

Also more specifically, an important embodiment of the present inventionis a compatibilized product comprising a mixture of polyethylene glycol(PEG) with polyether polyols such as, for example, polytetramethyleneether glycol (PTMEG) and/or polypropylene glycol (PPG), at thesetemperatures.

DETAILED DESCRIPTION

As a result of intense research in view of the above, we have found thatwe can manufacture novel compatibilized products comprising two or moreotherwise immiscible organic materials, i.e. compounds, saidcompatibilized products being stable in the liquid phase at temperaturesranging from about 40° C. to about 200° C., more specifically from about50° C. to about 100° C., depending on the phase separation transitionand decomposition temperatures of the individual components of thecompatibilized product, by a method comprising use of a glycol derivedfrom polymerization of alkylene oxide and tetrahydrofuran, the alkyleneoxide having from 2 to 4 carbon atoms, i.e.poly(tetramethylene-co-alkyleneether) glycol, especially such acopolymer specially manufactured as herein described. The glycols foruse herein, also referred to as alkylene oxide copolymers, are derivedfrom polymerization of alkylene oxide having from 2 to 4 carbon atomsand THF. Non-limiting examples of such alkylene oxide copolymers for useherein include the poly(tetramethylene-co-alkyleneether) glycols derivedfrom one alkylene oxide, e.g. ethylene oxide (EO), molecule and two THFmolecules; one alkylene oxide, e.g. EO, molecule and three THFmolecules, etc.

As used herein, the term “polymer” refers to the product of apolymerization reaction, and is inclusive of homopolymers, copolymers,terpolymers, etc.

As used herein, unless specified otherwise, the term “copolymer(s)”refers to polymers formed by the polymerization of at least twodifferent monomers. For example, the term “copolymer” includes thecopolymerization reaction product of ethylene and an alpha-olefin(α-olefin), such as by way of example propylene and 1-hexene, or analkylene oxide such as ethylene oxide and tetrahydrofuran. However, theterm “copolymer” is also inclusive of for example, the copolymerizationof a mixture of ethylene, propylene, 1-hexene, and 1-octene, or amixture of various alkylene glycols and tetrahydrofuran.

As used herein, mole percent (“mole %”), unless noted otherwise, means apercent of a particular component based on the total moles of themixture containing the component. For example, if a mixture containsthree moles of compound A and one mole of compound B, then the compoundA comprises 75 mole % of the mixture and the compound B comprises 25mole %. This theory applies for designations of weight percent (“wt. %”)as well.

As used herein, the term “phase separation transition temperature” meansthe temperature at which a component of the novel compatibilized productcomposition of the present invention separates from the stable liquidphase at atmospheric pressure. For example, U.S. Pat. No. 4,492,613teaches that the phase separation transition temperature for methanoland cyclohexane (50:50 weight ratio) at atmospheric pressure is about40° C.

As used herein, the term “compatibilizing” means manufacturing by themethod of the present invention a stable homogeneous mixture of two ormore otherwise generally immiscible organic compounds. The term“compatibilized product” means a stable homogeneous mixture of two ormore otherwise generally immiscible organic compounds made by the methodof the present invention. The term “stable” means not changing form,phase or chemical nature in the liquid phase at temperatures rangingfrom about 40° C. to about 200° C., more specifically from about 50° C.to about 100° C., depending on the phase separation transition anddecomposition temperatures of the individual components of thecompatibilized product.

The novel compatibilized product composition of the present inventioncomprises from about 10 to about 45 wt. %, for example, from about 12 toabout 40 wt. %, of one or a mixture of first organic compounds, such as,for example, short chain glycols; from about 10 to about 45 wt. %, forexample, from about 12 to about 40 wt. %, of one or a mixture of other,i.e. second, organic compounds generally immiscible with said firstorganic compounds, such as, for example, long chain polyols, and fromabout 10 to about 80 wt. %, for example, from about 20 to about 76 wt.%, of a glycol derived from polymerization of an alkylene oxide, forexample alkylene oxide of from 2 to 4 carbon atoms, e.g. ethylene oxide(EO), a propylene oxide or a butylene oxide, and tetrahydrofuran (THF),especially such a copolymer specially manufactured as herein described.

The copolymer of alkylene oxide and tetrahydrofuran, i.e.poly(tetramethylene-co-alkyleneether) glycol, required for use hereinmay be manufactured by the process comprising contacting a solution of68 to 94 parts tetrahydrofuran, 5 to 30 parts alkylene oxide, e.g.ethylene oxide, and 0.2 to 1.5 parts compound containing reactivehydrogen atoms, e.g. water, with a polymerization catalyst, e.g. an acidpolymerization catalyst, such as, for example, a polymeric catalystwhich contains sulfonic acid groups as described below, in a continuousstirred tank reactor held at a temperature of from about 40 to about 80°C., followed by distilling off the unreacted tetrahydrofuran, alkyleneoxide and other volatile byproducts, filtering to remove any catalystfines and other solids present, and then distilling off the oligomericcyclic ether by-products, and recovering thepoly(tetramethylene-co-alkyleneether) glycol.

Advantageously, the alkylene oxide copolymer of alkylene oxide andtetrahydrofuran, i.e. poly(tetramethylene-co-alkyleneether) glycol,required for use herein is manufactured by the process comprising:

a) polymerizing tetrahydrofuran and at least one alkylene oxide havingfrom 2 to 4 carbon atoms in the presence of an acid catalyst and atleast one compound containing reactive hydrogen atoms at a temperatureof from about 40° C. to about 80° C., for example, from about 56° C. toabout 72° C., to produce a polymerization product mixture comprisingalkylene oxide copolymer, copolyether glycol, at least one dimer of thealkylene oxide, and tetrahydrofuran;

b) separating a majority of the tetrahydrofuran and at least a portionof the dimer of the alkylene oxide from the polymerization productmixture of step a) to produce a crude product mixture comprisingalkylene oxide copolymer and copolyether glycol;

c) separating at least a portion of the alkylene oxide copolymer fromthe crude product mixture of step b) to produce an alkylene oxidecopolymer stream comprising alkylene oxide copolymer, i.e.poly(tetramethylene-co-alkyleneether) glycol, and a stream comprisingcopolyether glycol; and

d) recovering the alkylene oxide copolymer stream of step c) and,optionally, recycling at least a portion of the recovered alkylene oxidecopolymer stream to the polymerization step a).

In the above process, the alkylene oxide may be selected from, forexample, the group consisting of ethylene oxide; 1,2-propylene oxide;1,3-propylene oxide; 1,2-butylene oxide; 2,3-butylene oxide;1,3-butylene oxide and combinations thereof. The compound containingreactive hydrogen atoms may be selected, for example, from the groupconsisting of water; ethylene glycol; 1,3-propanediol; 1,4-butanediol;neopentyl glycol; poly(tetramethylene ether) glycol having a molecularweight of from about 130 dalton to about 400 dalton, for example, fromabout 200 dalton to about 300 dalton; copolyether glycols having amolecular weight of from about 130 dalton to about 400 dalton, forexample, from about 200 dalton to about 300 dalton; and combinationsthereof. In this process, the preferred compound containing reactivehydrogen atoms is water. In this process, if the alkylene oxidecomprises ethylene oxide, the dimer of the alkylene oxide will comprise1,4-dioxane, and the temperature of step a) will, for example, be fromabout 56° C. to about 72° C.

In the above process, the acid catalyst may be, for example, selectedfrom the group consisting of acidified natural or synthetic zeolites,acidified zirconium/tin sulfate compounds, compounds comprising at leastone catalytically active hydrogen-containing molybdenum and/or tungstenmoiety applied to an oxidic support, polymeric catalysts which containsulfonic acid groups and combinations thereof. The acidified zeolitesfor use herein are exemplified by faujasite (described in EP-A 492807),zeolite Y, zeolite Beta (described in U.S. Pat. No. 3,308,069), ZSM-5(described in U.S. Pat. No. 3,702,886), MCM-22 (described in U.S. Pat.No. 4,954,325), MCM-36 (described in U.S. Pat. No. 5,250,277), MCM-49(described in U.S. Pat. No. 5,236,575), MCM-56 (described in U.S. Pat.No. 5,362,697), PSH-3 (described in U.S. Pat. No. 4,439,409), SSZ-25(described in U.S. Pat. No. 4,826,667) and the like. The acidifiedzirconium/tin sulfate compounds for use herein are exemplified bysulfated zirconia as illustrated in U.S. Pat. No. 5,149,862. Thecompounds comprising at least one catalytically activehydrogen-containing molybdenum and/or tungsten compound applied to anoxidic support are exemplified by H₃PW₁₂O₄₀ and H₄SiMo₁₂O₄₀ as describedin Chem. Rev. 1998, 98, p 171-198. The polymeric catalysts which containsulfonic acid groups for use herein are exemplified by theperfluorinated sulfonic acid resins as illustrated in U.S. Pat. No.3,282,875. The preferred polymeric catalyst which contains sulfonic acidgroups comprises a perfluorocarbon backbone and the side chain isrepresented by the formula:—O—CF₂CF(CF₃)—O—CF₂CF₂SO₃Xwherein X is H. Polymers of this latter type are disclosed in U.S. Pat.No. 3,282,875, and can be made by copolymerization oftetrafluoroethylene (TFE) and the perfluorinated vinyl etherCF₂═CF—O—CF₂CF(CF₃)—O—CF₂CF₂SO₂F,perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) (PDMOF),followed by conversion to sulfonate groups by hydrolysis of the sulfonylfluoride groups, and acid exchanged as necessary to convert to thesulfonic acid form. The perfluorinated sulfonic acid resin may bepretreated (hydrotreated) by placing it along with deionized water at aweight ratio of resin/water of from about ¼ to about 1/10 into a cleanstainless steel autoclave, heating to a temperature of, for example,from about 170° C. to about 210° C. under agitation, and holding at thattemperature for up to about 12 hours, for example from about 1 hour toabout 8 hours.

In the above process, the tetrahydrofuran component may further compriseat least one alkyltetrahydrofuran selected from the group consisting of2-methyltetrahydrofuran, 3-methyltetrahydrofuran,3-ethyltetrahydrofuran, and combinations thereof.

In the above process for manufacture of the alkylene oxide copolymer ofalkylene oxide and tetrahydrofuran, i.e.poly(tetramethylene-co-alkyleneether) glycol, for use herein, theseparation of step b) may be accomplished by generally acceptedseparation technology, and may comprise at least one distillation, andthe separation of step c) may be accomplished by generally acceptedseparation technology, and may comprise an operation selected from thegroup consisting of short-path distillation, film evaporation, flashevaporation, solvent extraction and combinations thereof.

The above process may further comprise separating at least a portion ofthe tetrahydrofuran obtained in step b) from the dimer of the alkyleneoxide copolymer obtained in step b), and optionally recycling at least aportion of the tetrahydrofuran so obtained to the polymerization stepa). This separation may be accomplished by generally accepted separationtechnology.

In the above process, when the alkylene oxide is ethylene oxide, anespecially useful glycol derived from ethylene oxide and tetrahydrofuranis manufactured.

In this later process situation, alkylene oxide copolymer of ethyleneoxide and tetrahydrofuran, i.e. poly(tetramethylene-co-ethyleneether)glycol, especially useful herein, is manufactured by the steps of:

a) polymerizing tetrahydrofuran and ethylene oxide in the presence of anacid catalyst described above, for example, a polymeric catalyst whichcontains sulfonic acid groups, and at least one compound containingreactive hydrogen atoms selected from the group consisting of water,1,4-butanediol, poly(tetramethylene ether) glycol having a molecularweight of from about 130 dalton to about 400 dalton, for example, fromabout 200 dalton to about 300 dalton, andpoly(tetramethylene-co-ethyleneether) glycol having a molecular weightof from about 130 dalton to about 400 dalton, for example, from about200 dalton to about 300 dalton, for example, water, in the temperaturerange of from about 50° C. to about 80° C., for example, from about 56°C. to about 72° C., to produce a polymerization product mixturecomprising alkylene oxide copolymer, i.e.poly(tetramethylene-co-ethyleneether) glycol, copolyether glycol,1,4-dioxane, and tetrahydrofuran;

b) separating a majority of the tetrahydrofuran and at least a portionof the 1,4-dioxane from the polymerization product mixture of step a) toproduce a crude product mixture comprising alkylene oxide copolymer andcopolyether glycol;

c) separating at least a portion of the alkylene oxide copolymer fromthe crude product mixture of step b) to produce an alkylene oxidecopolymer stream comprising alkylene oxide copolymer and a streamcomprising copolyether glycol; and

d) recovering the alkylene oxide copolymer stream of step c) and,optionally, recycling at least a portion of the recovered alkylene oxidecopolymer stream to the polymerization step a).

In the later process situation, the tetrahydrofuran component mayfurther comprise at least one alkyltetrahydrofuran selected from thegroup consisting of 3-methyltetrahydrofuran, 3-ethyltetrahydrofuran andcombinations thereof. In this later process situation, the separation ofstep b) may be accomplished by generally accepted separation technology,and may comprise at least one distillation, and the separation of stepc) may be accomplished by generally accepted separation technology, andmay comprise an operation selected from the group consisting ofshort-path distillation, film evaporation, flash evaporation, solventextraction and combinations thereof. The later process situation mayfurther comprise separating at least a portion of the tetrahydrofuranobtained in step b) from the 1,4-dioxane obtained in step b) bygenerally accepted separation technology, and optionally recycling atleast a portion of the tetrahydrofuran so obtained to the polymerizationstep a).

The method of the present invention for manufacturing a stablehomogeneous mixture of two or more otherwise generally immiscibleorganic components, i.e. compounds, involves the steps of (1) combiningor mixing the generally immiscible organic components with the alkyleneoxide copolymer, i.e. the poly(tetramethylene-co-alkyleneether) glycol,as manufactured above, in a vessel, (2) heating the combination ormixture of step (1) at a temperature at which all materials are liquid(typically from about 35° C. to about 65° C., for example, from about40° C. to about 60° C., to form a compatibilized, single-phase productstable in the liquid phase at a temperature of from about 40° C. toabout 200° C., and (3) recovering the compatibilized, single-phaseproduct stable in the liquid phase at a temperature of from about 40° C.to about 200° C. The combination of step (1) comprises from about 10 toabout 45 wt. %, for example, from about 12 to about 40 wt. %, firstorganic compound(s), such as, for example, short chain glycols; fromabout 10 to about 45 wt. %, for example, from about 12 to about 40 wt.%, other, i.e. second, organic compound(s) generally immiscible withsaid first organic compound(s), such as, for example, long chainpolyols; and from about 10 to about 80 wt. %, for example, from about 20to about 76 wt. %, of the alkylene oxide copolymer, e.g.poly(tetramethylene-co-ethyleneether) glycol.

For recovered product testing purposes, once the combination of step (1)has been heated at the required temperature in step (2), a visualdetermination of homogeneity of the recovered step (3) product can bemade by shaking the recovered product in an appropriate vessel.Immiscible mixtures will appear hazy or multi-phased. This visualdetermination test may be a “yes/no” determination in which the presenceor absence of two of more layers or turbidity in the shaken sample is anindication of miscibility (yes) versus immiscibility (no). The number ofphases can also be identified, as done hereinbelow. Similar homogeneitydeterminations were used in U.S. Pat. Nos. 4,226,757, 4,385,133,6,063,308, and 6,093,342.

The novel compatibilized product of the present invention and blends ormixtures comprising same, may further comprise, if desired, an effectiveamount of a stabilizer, such as, for example, to prevent colorformation. Many such stabilizers are known in the art, any of which maybe used with the presently disclosed compatibilized product. Among thestabilizers available for use with the present invention are phosphorusoxo acids, acid organo phosphates, acid phosphate metal salts, acidicphosphate metal salts and combinations thereof.

The novel compatibilized product of the present invention and blends ormixtures comprising same, may further comprise, if desired, an effectiveamount of a colored pigment. Many colored pigments for use with theproduct of the present invention and mixtures comprising same are knownin the art, any of which may be used. Among the pigments available foruse with the present invention are carbon black, phthalocyanine blues,phthalocyanine greens, anthraquinone dyes, scarlet 2b Lake, azocompounds, acid azo pigments, quinacridones, chromophthalocyaninepyrrols, halogenated phthalocyanines, quinolines, heterocyclic dyes,perinone dyes, anthracenedione dyes, thiozanthene dyes, parazolone dyes,polymethine pigments and combinations thereof.

The novel compatibilized product of the present invention and blends ormixtures comprising same, may also be combined, if desired, with otheror additional additives or compounds to provide the compositions withparticular, desirable characteristics. Many such additives and compoundsare known in the art. The use of appropriate additives or compounds iswell within the skill of one in the art. Examples of such other oradditional additives or compounds include UV stabilizers, anti-oxidants,light stabilizers, flame retardants, antistatic agents, biocides,fragrances, viscosity-breaking agents, impact modifiers, plasticizers,fillers, reinforcing agents, lubricants, mold release agents, blowingagents, nucleating agents and the like.

EXAMPLES

The presently described and claimed method and compatibilized productwill be understood more fully by reference to the Examples below withoutintention of restricting the scope of the present claims.

Example 1

A poly(tetramethylene-co-ethyleneether) glycol sample with about 40 mole% ethyleneether units and 1000 dalton molecular weight was prepared bycontacting a solution of 89.4 parts THF, 9.7 parts ethylene oxide, and0.9 parts water with a polymeric catalyst which contains sulfonic acidgroups as described above, hydrotreated as described above, in acontinuous stirred tank reactor held at 58° C., followed by distillingoff the unreacted THF and ethylene oxide, filtering to remove anycatalyst fines present, and then distilling off the cyclic etherby-products and recovering poly(tetramethylene-co-ethyleneether) glycol.

Example 2

A poly(tetramethylene-co-ethyleneether) glycol sample with about 50 mole% ethyleneether units and 1000 dalton molecular weight was prepared bycontacting a solution of 79.5 parts THF, 19.2 parts ethylene oxide, and1.3 parts water with polymeric catalyst which contains sulfonic acidgroups as described above, hydrotreated as described above, in acontinuous stirred tank reactor held at 58° C., followed by distillingoff the unreacted THF and ethylene oxide, filtering to remove anycatalyst fines present, and then distilling off the cyclic etherby-products and recovering poly(tetramethylene-co-ethyleneether) glycol.

Example 3

Twelve separate mixtures of PTMEG having an average molecular weight ofabout 1,000 (Component a), ethylene glycol (Component b), andpoly(tetramethylene-co-ethyleneether) glycol prepared as in Example 1containing about 40 mole % ethylene oxide-derived units and having anaverage molecular weight of about 1,000 (Component c), were combined inclear glass containers in the approximate weight fraction proportionsshown in Table 1, and the mixtures were placed in an oven heated at 50°C. After one hour in the oven the mixtures were observed and a visualdetermination of homogeneity at 40° C. was made as indicated above.

TABLE 1 No. of phases Reference Component a Component b Component c at@40° C. 3-1 0.33 0.33 0.33 1 3-2 0.50 0.00 0.50 1 3-3 0.50 0.50 0.00 23-4 0.17 0.17 0.67 1 3-5 1.00 0.00 0.00 1 3-6 1.00 0.00 0.00 1 3-7 0.000.50 0.50 1 3-8 0.00 1.00 0.00 1 3-9 0.67 0.17 0.17 1 3-10 0.17 0.670.17 2 3-11 0.00 1.00 0.00 1 3-12 0.00 0.00 1.00 1

Example 4

Seventeen separate mixtures of PTMEG having an average molecular weightof about 1,000 (Component a), butanediol (Component b), andpoly(tetramethylene-co-ethyleneether) glycol prepared as in Example 1containing about 40 mole % ethylene oxide-derived units and having anaverage molecular weight of about 1,000 (Component c), were combined inclear glass containers in the approximate weight fraction proportionsshown in Table 2, and the mixtures were placed in an oven heated at 50°C. After one hour in the oven the mixtures were observed and a visualdetermination of homogeneity at 40° C. was made as indicated above.

TABLE 2 No. of phases Reference Component a Component b Component c at@40° C. 4-1 0.33 0.33 0.33 1 4-2 0.50 0.00 0.50 1 4-3 0.50 0.50 0.00 24-4 0.17 0.17 0.67 1 4-5 1.00 0.00 0.00 1 4-6 1.00 0.00 0.00 1 4-7 0.000.50 0.50 1 4-8 0.00 1.00 0.00 1 4-9 0.67 0.17 0.17 1 4-10 0.17 0.670.17 2 4-11 0.00 1.00 0.00 1 4-12 0.00 0.00 1.00 1 4-13 0.75 0.25 0 24-14 0.25 0.75 0 2 4-15 0.50 0.25 0.25 1 4-16 0.25 0.50 0.25 2 4-17 0.000.75 0.25 2

Example 5

Twenty-three separate mixtures of PTMEG having an average molecularweight of about 1,000 (Component a), polyethylene glycol (Component b),and poly(tetramethylene-co-ethyleneether) glycol copolymer prepared asin Example 1 containing about 40 mole % ethylene oxide-derived units andhaving an average molecular weight of about 1,000 (Component c), werecombined in clear glass containers in the approximate weight fractionproportions shown in Table 3, and the mixtures were placed in an ovenheated at 50° C. After one hour in the oven the mixtures were observedand a visual determination of homogeneity at 40° C. was made asindicated above.

TABLE 3 No. of phases Reference Component a Component b Component c at@40° C 5-1 0.33 0.33 0.33 1 5-2 0.50 0.00 0.50 1 5-3 0.50 0.50 0.00 25-4 0.17 0.17 0.65 1 5-5 1.00 0.00 0.00 1 5-6 1.00 0.00 0.00 1 5-7 0.000.50 0.50 1 5-8 0.00 1.00 0.00 1 5-9 0.66 0.17 0.17 1 5-10 0.17 0.660.17 2 5-11 0.00 1.00 0.00 1 5-12 0.00 0.00 1.00 1 5-13 0.35 0.65 0.00 25-14 0.18 0.66 0.16 2 5-15 0.00 0.70 0.30 1 5-16 0.51 0.30 0.19 1 5-170.00 1.00 0.00 1 5-18 0.18 0.82 0.00 2 5-19 0.70 0.30 0.00 2 5-20 0.510.47 0.02 2 5-21 0.70 0.30 0.00 2 5-22 0.24 0.46 0.30 1 5-23 0.00 0.850.15 1

Example 6

Twenty-one separate mixtures of a polyol (Component a) and an immiscibleshort or long chain glycol (Component b) were combined in clear glasscontainers in the approximate weight fraction proportions shown in Table4, and the mixtures were placed in an oven heated at 50° C. After onehour in the oven the mixtures were observed and a visual determinationof homogeneity at 40° C. was made as indicated above. To the mixtureswas added a portion of poly(tetramethylene-co-ethyleneether) glycolcopolymer prepared as in Example 2 containing about 50 mole % ethyleneoxide-derived units and having an average molecular weight of about1,000 (Component c). In Table 4, components “a” and “b” are abbreviatedas follows: “a1” is a 1000 MW polytetramethylene ether glycolmanufactured by INVISTA S.a.r.l. under the trade name Terathane®(T1000), “a2” is a 2000 MW polytetramethylene ether glycol manufacturedby INVISTA S.a.r.l. under the trade name Terathane® (T2000), “a3” ispolypropylene glycol, “a4” is polycaprolactone glycol and “a5” is a 2000MW polyethylenebutylene adipate manufactured by Chemtura Corp. under thetrade name Formrez® E2454 (E2454); and “b1” is ethylene glycol, “b2” is1,3-propanediol (PDO), “b3” is 1,4-butanediol, “b4” is the 1000 MWpolytetramethylene ether glycol T1000, “b5” is the 2000 MWpolyethylenebutylene adipate E2454 and “b6” is polypropylene glycol.Component “c” is the poly(tetramethylene-co-ethyleneether) glycolcopolymer prepared as in Example 2.

TABLE 4 Components Components a/b/c Weight Ratio Ref. a b c 50/50/0037.5/37.5/25 25/25/50 12.5/12.5/75 6-1 a1 b1 c 2 2 1 6-2 a1 b2 c 2 2 16-3 a1 b3 c 2 1 6-4 a2 b1 c 2 2 2 2 6-5 a2 b2 c 2 2 2 2 6-6 a2 b3 c 2 22 1 6-7 a3 b1 c 2 2 1 6-8 a3 b2 c 2 2 1 6-9 a3 b3 c 2 2 1 6-10 a4 b1 c 16-11 a4 b2 c 2 2 1 6-12 a4 b3 c 2 2 1 6-13 a5 b1 c 2 2 2 2 6-14 a5 b2 c2 2 2 2 6-15 a5 b3 c 2 2 2 2 6-16 a3 b4 c 1 6-17 a4 b5 c 1 6-18 a4 b6 c1 6-19 a4 b4 c 1 6-20 a5 b6 c 2 2 2 2 6-21 a5 b4 c 2 2 2 2

Example 7

Five separate mixtures of a polyol (Component a) and polyethylene glycol(Component b) were combined in clear glass containers in the approximateweight fraction proportions shown in Table 5, and the mixtures wereplaced in an oven heated at 50° C. After one hour in the oven themixtures were observed and a visual determination of homogeneity at 40°C. was made as indicated above. To the mixture was added a portion ofpoly(tetramethylene-co-ethyleneether) glycol copolymer prepared as inExample 2 containing about 50 mole % ethylene oxide-derived units andhaving an average molecular weight of about 1,000 (Component c). InTable 5, components are abbreviated as in Example 6 and Table 4.

TABLE 5 Components Components a/b/c Weight Ratio No. a b c 50/50/0037.5/37.5/25 25/25/50 12.5/12.5/75 7-1 a1 PEG c 2 1 7-2 a2 PEG c 2 2 17-3 a3 PEG c 2 2 1 7-4 a4 PEG c 1 7-5 a5 PEG c 1

Example 8

A mixture of polyethylene glycol (1931 MW) and polyols was prepared andheated at 50° C. When thermal equilibrium was reached, the blend wasdegassed, combined with sufficient diisocyante (Dow Isonate® 181),curative (BDO), and catalyst (Dabco® 131) to produce elastomers of thedesired hard segment content (Table 6). “EOTHF” ispoly(tetramethylene-co-ethyleneether) glycol copolymer prepared as inExample 2. The combined materials were transferred to a mold and curedat 100° C. for 16 hours. After an additional 2 weeks at roomtemperature, the elastomers were tested for equilibrium water swellusing a procedure equivalent to ASTM D570.

TABLE 6 Reference 8-1 8-2 PTMEG (2027 MW) 25 25 PEG (1931 MW) 25 25EOTHF (50% EO, 964 MW) 50 — PTMEG (970 MW) — 50 Homogeneous @ 50° C. YesNo Isonate ® 181 (360.4 MW) 72 72 BDO (90 MW) 10 10 Dabco ® 131 .006.006 Weight increase, % (ASTM D570) 24% 12%

Example 9

A mixture of polyethylene glycol (966 MW) and polyols was prepared andheated at 50° C. When thermal equilibrium was reached, the blend wasdegassed, combined with sufficient diisocyante (Dow Isonate® 181),curative (BDO), and catalyst (Dabco® 131) to produce elastomers of thedesired hard segment content (Table 7). “EOTHF” ispoly(tetramethylene-co-ethyleneether) glycol copolymer prepared as inExample 2. The combined materials were transferred to a mold and curedat 100° C. for 16 hours. After an additional 2 weeks at roomtemperature, the elastomers were tested for water uptake.

TABLE 7 Reference 9-1 9-2 PTMEG (970 MW) 25 75 PEG (966 MW) 25 25 EOTHF(50% EO, 964 MW) 50 — PTMEG (970 MW) — 50 Homogeneous @ 50° C. Yes NoIsonate ® 181 (360.4 MW) 74 74 BDO (90 MW) 8.2 8.2 Dabco ® 131 .005 .005Weight increase, % (ASTM D570) 15% 10%

All patents, patent applications, test procedures, priority documents,articles, publications, manuals, and other documents cited herein arefully incorporated by reference to the extent such disclosure is notinconsistent with this invention and for all jurisdictions in which suchincorporation is permitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.

While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and may be readily made by thoseskilled in the art without departing from the spirit and scope of theinvention. Accordingly, it is not intended that the scope of the claimshereof be limited to the examples and descriptions set forth herein butrather that the claims be construed as encompassing all the features ofpatentable novelty which reside in the present invention, including allfeatures which would be treated as equivalents thereof by those skilledin the art to which the invention pertains.

The invention claimed is:
 1. A stable compatibilized mixture consistingof two or more immiscible organic compounds and from about 10 to about80 wt. % glycol derived from polymerization of alkylene oxide havingfrom 2 to 4 carbon atoms and tetrahydrofuran, said stable compatibilizedmixture being stable in the liquid phase at a temperature of from about40° C. to about 200° C., wherein said immiscible organic compoundsconsist of a first organic compound selected from the group consistingof short chain glycols, polyethers and mixtures thereof, and a secondorganic compound selected from the group consisting of long chainpolyols, polyesters and mixtures thereof.
 2. The stable compatibilizedmixture of claim 1 wherein the alkylene oxide is ethylene oxide.
 3. Thestable compatibilized mixture of claim 1 which is stable in the liquidphase at a temperature of from about 50° C. to about 100° C.
 4. Thestable compatibilized mixture of claim 1 wherein said first organiccompound is selected from the group consisting of ethylene glycol,polyethylene glycol, polypropylene glycol, butanediol and mixturesthereof, and said second organic compound is a polyether polyol.
 5. Thestable compatibilized mixture of claim 1 wherein said first organiccompound is selected from the group consisting of ethylene glycol,butanediol and mixtures thereof, and said second organic compound isselected from the group consisting of polytetramethylene ether glycol,polypropylene glycol, polycaprolactone glycol and a mixture thereof. 6.The stable compatibilized mixture of claim 1 wherein said first organiccompound is polyethylene glycol, and said second organic compound isselected from the group consisting of polytetramethylene ether glycol,polypropylene glycol and a mixture thereof.
 7. The stable compatibilizedmixture of claim 1 wherein from about 10 to about 45 wt. % of one or amixture of said first organic compounds are present and from about 10 toabout 45 wt. % of one or a mixture of said second organic compoundsimmiscible with said first organic compounds are present.